Silver halide containing pyrazolone magenta coupler

ABSTRACT

A magenta coupler having the general formula:   IS CONSPICUOUSLY SUPERIOR TO THE KNOWN MAGENTA COUPLER IN HEAT RESISTANCE AND MOISTURE RESISTANCE AND CAUSE LITTLE YELLOWING AND STAIN OF GROUND AND MOREOVER IS HIGH IN SOLUBILITY IN ORGANIC SOLVENTS.

United States Patent 1191 Yamada et al.

[451 July 29,1975

Japan [73] Assignee: Mitsubishi Paper Mills, Ltd., Tokyo,

Japan [22] Filed: May 10, 1974 [21] Appl. No.: 468,995

[30] Foreign Application Priority Data May 11, 1973 Japan 48-52395 [52] US. Cl 96/100; 260/310 [51] Int. Cl. G03C 1/40 [58] Field of Search 96/100, 56.5

[56] References Cited UNITED STATES PATENTS 2,600,788 6/1952 Loria et al. 96/100 3,580,722 5/1971 Sakamoto et a]. 96/100 3,676,137 7/1972 Mizuki et a1. 96/100 Primary Examiner-J. Travis Brown Attorney, Agent, or FirmCushman, Darby & Cushman [5 7] ABSTRACT A magenta coupler having the general formula:

A O l CONE COll'H C CH 11 l 2 N\ /CO R0 N Oi C15 is conspicuously superior to the known magenta coupler in heat resistance and moisture resistance and cause little yellowing and stain of ground and moreover is high in solubility in organic solvents.

3 Claims, Ne Drawings SILVER HALIDE CONTAINING PYRAZOLONE MAGENTA COUPLER BACKGROUND OF THE INVENTION Requirements for the protect type magenta coupler being practically usable are: (l) the coupler must have excellent color forming ability and formed dye must have excellent spectral absorption properties, (2) the coupler and the dye must have fastness to moisture, heat and light and especially they must cause no discoloration of color printing paper or film while being preserved, and (3) the coupler and the dye must be highly soluble in organic solvents such as dibutyl phthalate, ethyl acetate, etc. and must not be crystallized after they are dispersed in silver halide emulsion and the dispersion is coated on a support and dried. None of the hitherto known magenta couplers have fully satisfied said requirements. For example, the following coupler disclosed in British Patent No. 680,488 has high melting point, and low solubility in a coupler solvent and the dyes obtained by color development has the absorption maximum at 545 nm to cause formation of blue-rich magenta color image and to make it difficult to reproduce bright red color.

1; H OCH CONH CONH tC H SUMMARY OF THE INVENTION The inventors have made intensive research in an attempt to obtain excellent magenta couplers which satisfy said requirements. As the result, they have found that magenta couplers represented by the following general formula:

A-O-L-CONH CON'H c CH2 If i .20 R0 \N/ Cfl (wherein R is an alkyl group having 48 carbon atoms, A is phenyl group having at least one alkyl substituents, total number of carbon atoms in said alkyl substituents being 10 or more and L is an alkylene or alkyl substituted alkylene) satisfy said requirements and color photographic photosensitive materials containing said coupler are excellent. As the alkylene indicated by L, methylene is most preferred. That is, said couplers of the present inven- C II N spectral absorption properties advantageous for reproduction of color. Thus, color which substantially corresponds to original color can be attained.

Amount of the coupler of the present invention added to emulsion has no special limitation, but is preferably 20-600 g per one mol of silver halide. However, the amount varies depending upon the purpose of use and is not necessarily limited to said range and may be optionally changed.

3,897,254 3 4 PREFERRED EMBODIMENTS OF THE Typ ical exampleg of the coupler 6f the present in- INVENTION vention are as followsz w tC H Q- OCHCONII M I d N 00 (1) t-C H p I CONE-C CH,

OCHCON'H CONH C --CH 0 11 I: M 0050mm Cl C! CH5 OCH2CONH CONH if f N l2 N/ n-C H 0 001m c CH 11 o(c 1 coNH H 2 t-C H n-C H O at oz fa 3 tC H ocncozrr: cor-m (3H2 N 00 ('l) t-CJ-I J r N n---C H O or oz Examples of preparation of said compounds (1) and Step 2:

(2) are shown below.

Preparation EXAMPLE 1 Preparation of the Compound (1), namely, l-(2,4',6-trichlorophenyl)-3-{3"-n-a-(2", 4"-

di-tert-amylphenoxy) butyramido-4' -n-butoxybenzamido} 5 -pyrazolone tain 4.56 g of crystal having a melting point of l48.5-149.5C.

Preparation of 3-{n-a-(2',4-di-tert-amylphenoxy) butyramido}-4-n-butoxy benzoylchloride.

7 ml of thionyl chloride was added to 3.38 g of 3-{na-(2',4-di-tert-amylphenoxy) butyramido}-4-nbutoxybenzoic acid and these were refluxed for 2 hours. Excess thionyl chloride was distilled out therefrom on a water bath in vacuo and the resultant residue was used as it was for the following reaction.

Step 3:

Preparation of l-(2,4',6-trichlorophenyl)-3-{3-na-(2",4"-di-tert-amylphenoxy) butyramido-4-nbutoxybenzamido}-5-pyrazolone.

1.67 g of 1-(2',4,6-trichlorophenyl)-3-amino-5- pyrazolone was dissolved in 30 ml of dry acetonitrile. To the resultant solution was added dropwise over a period of 10 minutes a solution obtained by dissolving 3.5 g of 3-{n-a-(2',4'-di-tert-amylphenoxy) butyramido}- 4-n-butoxybenzoylchloride obtained in the step 2 in 20 ml of dried acetonitrile while refluxing and thereafter this was refluxed for 20 hours. Thereafter, acetonitrile was distilled out in vacuo and the resultant residue was recrystallized from methylcyclohexane to obtain 2.67 g of crystal having a melting point of l20l 25C. Elementary analysis of this crystal resulted in C:62.04%; H:6.44% and N:7.33%. (Calculated values for C H CI N O were as follows: C:62.2l%, H:6.40% and N:7.26%.

Preparation EXAMPLE 2 Preparation of Compound No. 2, namely, 1-(2',4',6-trichlorophenyl)-3-{3"-n-a-(2",4"-di-tertamylphenoxy) butyramido-4' -n-octyloxybenzamidol-S-pyrazolone.

Step 1:

Preparation of l-(2,4',6'-trichlorophenyl)-3-(4"-noctyloxy-3 '-nitrobenzamido )-5-pyrazolone.

5.57 g of l-(2',4',6'-trichlorophenyl)-3-amino-5- pyrazolone was dissolved in 60 ml of dry acetonitrile. To the resultant solution was added dropwise over a period of minutes a solution obtained by dissolving 6.9 g of 4-n-octyloxy-3-nitrobenzoylchloride in ml of acetonitrile while refluxing. Thereafter, this was refluxed for 4 hours. Undissolved material in hot state was filtered off and washed with hot methanol to obtain 9.5 g of crystal having a melting point of 27l-272C.

Step 2:

Preparation of l-(2,4,6-trichlorophenyl)-3-(4-noctyloxy-3 '-aminobenzamido)-5 -pyrazolone. To 80% acetic acid to which 3.44 g of iron powder was added was added dropwise over a period of 20 minutes under refluxing and stirring a solution obtained by dissolving 5.56 g of l-(2,4,6-trichlorophenyl)-3-(4"- n-octyloxy-3"-aminobenzamido)-5-pyrazolone in 40 ml of 80% acetic acid. Thereafter, this was refluxed with stirring for 2 hours. Hot undissolved material was filtered out and filtrate was concentrated in vacuo. The residual crystal was sufficiently washed with methanol to obtain 3.84 g of crystal having a melting point of 219220C.

Step 3:

Preparation of l(2',4',6'-trichlorophenyl)-3-{3"-na-(2",4"'-di-tert-amylphenoxy) butyramido-4"-noctyloxybenzamido}-5-pyrazolone.

1.58 g of l-(2,4',6'-trichlorophenyl)-3-(4"-noctyloxy-3'f-aminobenzamido)-5-pyrazolone was dissolved in 15 ml of dry acetonitrile. While refluxing, to the resultant solution was added dropwise over a period of 10 minutes a solution obtained by dissolving 1.22 g of n-a-(2,4-di-tert-amylphenoxy)-butyryl chloride in 15 ml of dry acetonitrile. Thereafter, this was refluxed for 11 hours, acetonitrolie was distilled out in vacuo and the residue was recrystallized from methylcyclohexane to obtain 1.28g of crystal having a melting point of l21.0123.5C. Elementary analysis of thus obtained crystal resulted in 064.08%, H:7.09% and N:6.66%. (Calculated values were 063.80%, l-l:6.94% and f0! C44H57CI3N405).

The following Examples prove that the coupler of the present invention has high solubility in organic solvents such as dibutylphthalate and ethyl acetate, shows little yellowing due to light, moisture and heat and that dyes formed by color development have excellent spectral absorption properties.

EXAMPLE 1 An emulsion was prepared in such a manner that molar ratio of silver halide and coupler was 2:1 and the Sodium hydroxide Sodium metaphosphate Sodium sulfite anhydrous Potassium bromide 4-Amino -N-ethyl-N-(B- methanesulfonamidoethyl)- m-toluidinesesquisulfate monohydrate Sodium hexamethaphosphate Hydroxylamine hydrochloride Benzyl alcohol Diethylene glycol Water to make 1 1 Then, the developed photosensitive material was bleach-fixed with a Ferric salt of EDTA bleach fix of the following compositions for 4 minutes.

Ferric salt of EDTA Sodium salt of EDTA Dibasic Ammonium thiosulfate Sodium sulfite anhydrous Sodium phosphate dibasic anhydrous Sodium bisulfate Water to make 1 l N0 N COMO UQUQ common Then, the fixed photosensitive material was washed with water for 8 minutes and thereafter was dipped in a solubilizing bath for 3 minutes and dried.

Spectral absorption curve of thus obtained magenta color image was obtained with a spectrophotometer (UV-200 manufactured by Shimazu Seisakusyo K.K.). The results are shown in Table 1. As comparative couplers, the following were employed: the known coupler l-(2,4,6-trichlorophenyl)-3-{3"-n-a (2"',4'"- ditert-amylphenoxy)butyramido-benzamido}-5- pyrazolone (Compound l-(2',4',6'- trichlorophenyl)-3-{ 3 '-n-a-(2 ,4' -di-tertamylphenoxy)butyramido-4"-methoxybenzamido}-5- pyrazolone [Compound (7)]; 1-(2,4',6- trichlorophenyl)-3-l 3-n-a-( 2 ',4' -di-tertamylphenoxy) butyramido-4"-chlorobenzamido}-5- pyrazolone [Compound (8)]; and l-(2',4',6- trichlorophenyl)-3 3 -n-a-( 2 ',4 '-di-tertamylphenoxy) butyramido-2 '-n-butoxybenzamide }-5- pyrazolone [Compound (9)]. [The compounds (7)(9) are couplers which are similar to the coupler of the present invention] Tab 1 v vsolubility was expressed by amount (ml) of ethyl acetate required for dissolving l g of the couplers at room Compound (1) (2) temperature.

Absorption maximum 539 537 546 544 548 549 Table 3 wave Y I length (nm).

- Compound Melting point Solubility These compounds are those outside the scope of the present invention.

(l) l20.0-l 250C 0.5 (2) l2l.0-l23.5C 0.5 10 (w l34.0-136.0C 1.0 As 18 clear from Table l, the magneta color images (7)* 232.0:-233.5:C 40 obtained using the couplers (l) and (2) of the present 53;: z'gg'g jg'g g 0 invention had wave lengths of absorption maximum hi h were sho ter than those of magenta color images "These compounds are those which are outside the scope ot'the present invention obtained using the comparative couplers (6), (7), (8) and (9). This fact proves that use ofthe couplerof the The couplers (I) and (2) of the present invention Present Invention can reproduce bnght red color had lower melting points and higher solubilities in ethyl EXAMPLE 2 acetate and in dibutyl phthalate than the comparative couplers. When the compounds (1) and (2) were used photosensitive materials Produced in the same 20 in photosensitive materials in the same manner as in Her as in Example 1 which were not exposed to light, Example 1, no crystals were, separated. Furthermore, but were subjected to developing treatments. Simila? to when these were dispersed in emulsion and were sub- Example 1, and to test for yellowing due to light jected toexperiment on change with lapse of time and heat to Obtain the results as Shown in Table under severe conditigns no crystals were separated 2. The numerical values in Table 2 represent increment d viscosity was t i d of absorption intensity to blue light. As a comparative Wh t i l i d i coupler, the known l-phenyl-3-{3a-(2,4"-di-tert- 1. A silver halide photographic emulsion comprising amylphcnoxy) acetamidobenzamide}-5-pyrazolone a silver halide and a magenta coupler having the follow- [Compound (10)]. ing general formula:

B lJ l C NH C CH 13 C H OCH COVH U O n 2 N v =0 A-O-L-CONH CONH-CCH ll l N GO RO N (L8 CZ Table 2 As is clear from Table 2, the photosensitive material containing the coupler of the present invention was sta- After exposure to After being maintained ble to light and humid heat, caused little yellowing and Comsun light for 2 at a humidity of 80% coloration of ground pound weeks and at 50C for 1 month EXAMPLE 3 82g 82g Melting point and solubility of couplers (l) and (2) of the present invention and of the comparative cou- This compound is one which is outside the scope of the present invention. plers used in the Example 1 are Shown in Table The wherein R is an alkyl group having 4-8 carbon atoms, tuted alkylenei Ais phenyl group having at least one alkyl substituent, 2. A silver halide emulsion according to claim 1 the total number of carbon atoms in said substituents I wherein the magenta coupler is selected from the folbeing at least 10 and L is an alkylene or alkyl substilowings:

fz s ocHoom cow C 11 I 1 II" I a N 00 (1) t-C h n-C H o 4 '9 oz Cl 92% t-C H OClICON'l-i com; g k c14 I N co (2) t-C H n c H o N 7 oz oz E2 5 ooncomi coma c CH l 2 N 00 (3 n C15H3l n-C H o oz cz $2 5 0 11 Q OCHCON'H CON'H (1 CH2 II I N c0 (4) n-C H O 8 17 N oz cz CH3 OCH CONl-I" CONH 'l I ;l 4 N C nC H \N 4 9 on C2 t-C H O(CH2)3CONH CON'H E: (3H2 N 00 (6) t-C H n-C H o emulsion of claim 1. 

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION COMPRISING A SILVER HALIDE AND A MAGENTA COUPLER HAVING THE FOLLOWING GENERAL FORMULA:
 2. A silver halide emulsion according to claim 1 wherein the magenta coupler is selected from the followings:
 3. A color photographic sensitive material comprising a support having thereon a layer of the silver halide emulsion of claim
 1. 